Reactive dyes, process for their preparation and their use

ABSTRACT

Reactive dyes of formula (1)                    
     wherein 
     A is phenyl or naphthyl, each of which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or a fiber-reactive group of formula (2 a ), (2 b ), (2 c ), (2 d ) or (2 e ) 
     
       
         —SO 2 —Y  (2 a ), 
       
     
     
       
         —NH—CO—(CH 2 ) l —SO 2 —Y  (2 b ), 
       
     
     
       
         —CONH—(CH 2 ) m —SO 2 —Y  (2 c ), 
       
     
     
       
         —NH—CO—CH(Hal)—CH 2 Hal  (2 d ) 
       
     
     or 
     
       
         —NH—CO—C(Hal)═CH 2   (2 e ), 
       
     
     B is an aliphatic linking group, 
     D is the radical of a diazo component of the benzene or naphthalene series, 
     R 1  is hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, 
     R 2  is hydrogen, cyano, carbamoyl or sulfomethyl, 
     R 3  is hydrogen or C 1 -C 4 alkyl, 
     R is hydrogen or unsubstituted or substituted C 1 -C 4 alkyl or corresponds to a radical of formula (3)                    
      wherein B, D, R 2  and R 3  have the meanings cited above, 
     X 1  is halogen, hydroxy, C 1 -C 4 alkoxy, unsubstituted or substituted C 1 -C 4 alkylthio or amino, or a N-heterocycle which may contain additional heteroatoms, 
     Hal is chloro or bromo, 
     Y is vinyl or a —CH 2 —CH 2 —U radical, U is a group a which is removable with alkali, and l and m are each independently of the other the number 2, 3 or 4, 
     with the proviso that A and D are not simultaneously a phenyl radical which is substituted by the radical of formula (2 a ) if R is β-hydroxyethyl or β-sulfatoethyl and R 1  is C 1 -C 4 alkyl, are particularly suitable for dyeing cotton and give dyeings having very good allround fastness properties.

The present invention relates to novel reactive dyes, to processes fortheir preparation and to their use for dyeing or printing fibrematerials.

The practice of dyeing with reactive dyes has given rise in recent timesto more stringent demands being made on the quality of the dyeings andon the economy of the dyeing process. For this reason, there is still aneed for novel reactive dyes with improved properties, especiallyapplication properties.

Dyeing today calls for reactive dyes which have sufficient substantivityand which at the same time have good washing off properties with respectto unfixed dye. In addition, the dyes shall have a good tinctorial yieldand high reactivity, and they shall also give, in particular, dyeingswith high degrees of fixation. The dyes of the prior art do not meetthese requirements in all respects.

This invention therefore has for its object to provide novel improvedreactive dyes for dyeing and printing fibre materials and which have theabove specified qualities to a high degree. The novel dyes shall bedistinguished in particular by excellent fixation yields and superiorfibre-dye bond stability, and further they shall have the property ofbeing easily washed off to remove unfixed dye. They shall also producedyeings with good allround fastness properties, for examplelightfastness and wetfastness.

It has been found that this object is substantially achieved with thenovel reactive dyes defined below.

This invention thus relates to reactive dyes of formula (1)

wherein

A is phenyl or naphthyl, each of which is unsubstituted or substitutedby halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, sulfo or a fibre-reactivegroup of formula (2a), (2b), (2c), (2d) or (2e)

—SO₂—Y  (2a),

—NH—CO—(CH₂)₁—SO₂—Y  (2b),

—CONH—(CH₂)_(m)—SO₂—Y  (2c),

—NH—CO—CH(Hal)—CH₂Hal  (2d)

or

—NH—CO—C(Hal)═CH₂  (2e),

B is an aliphatic linking group,

D is the radical of a diazo component of the benzene or naphthaleneseries,

R₁ is hydrogen or unsubstituted or substituted C₁-C₄alkyl,

R₂ is hydrogen, cyano, carbamoyl or sulfomethyl,

R₃ is hydrogen or C₁-C₄alkyl,

R is hydrogen or unsubstituted or substituted C₁-C₄alkyl or correspondsto a radical of formula (3)

wherein B, D, R₂ and R₃ have the meanings cited above,

X₁ is halogen, hydroxy, C₁-C₄alkoxy, unsubstituted or substitutedC₁-C₄alkylthio or amino, or a N-heterocycle which may contain additionalheteroatoms,

Hal is chloro or bromo,

Y is vinyl or a —CH₂—CH₂—U radical, U is a group a which is removablewith alkali, and l and m are each independently of the other the number2, 3 or 4,

with the proviso that A and D are not simultaneously a phenyl radicalwhich is substituted by the radical of formula (2a) if R isβ-hydroxyethyl or β-sulfatoethyl and R₁ is C₁-C₄alkyl.

The novel dyes of formula (1) are fibre-reactive. Fibre-reactivecompounds are to be understood as meaning compounds which are capable ofreacting with the hydroxyl groups of the cellulose, amino, carboxy,hydroxy or thiol groups in wool and silk, or with the amino and,optionally, with the carboxy groups of synthetic polyamides withformation of covalent chemical bonds.

In the novel reactive dyes of formula (1) at least one of the radicals Aand D contains a fibre-reactive group, or X₁ is halogen.

The dyes of formula (1) contain at least one, preferably 2 to 6 and,more preferably, 2 to 4, sulfo groups, which are either in the form oftheir free acid or, preferably, in the form of their salts. Suitablesalts are, for example, the alkali metal salts, alkaline earth metalsalts or ammonium salts, the salts of an organic amine, or mixturesthereof. Examples to be mentioned are the sodium, lithium, potassium orammonium salts, the salt of mono-, di- or tri-ethanolamine, or Na/Li— orNa/Li/NH₄ mixed salts.

R and R₁ defined as unsubstituted or substituted C₁-C₄alkyl may bemethyl, ethyl, n- or isopropyl or n-, sec-, tert- or isobutyl which isunsubstituted or substituted e.g. by hydroxy, sulfo, sulfato, carboxy,cyano, halogen, C₁-C₄alkoxycarbonyl or carbamoyl, preferably by hydroxy,sulfo, sulfato or carboxy.

R is preferably hydrogen, unsubstituted or hydroxy-substitutedC₁-C₄alkyl or a radical of formula (3), particularly preferablyhydrogen, methyl, ethyl or β-hydroxyethyl or a radical (3) and, veryparticularly preferably, hydrogen or a radical (3), wherein B, D, R₂ andR₃ have the meanings cited above. In a very particularly preferredembodiment of this invention, R is a radical of formula (3).

R₁ is preferably hydrogen or C₁-C₄alkyl, particularly preferablyhydrogen, methyl or ethyl and, very particularly preferably, hydrogen.

R₂ is preferably carbamoyl or sulfomethyl, more preferably carbamoyl.

R₃ defined as C₁-C₄alkyl is, for example, methyl, ethyl, n- or isopropylor n-, sec-, tert- or isobutyl, preferably methyl or ethyl.

R₃ is preferably methyl or ethyl, more preferably methyl.

R₂ is preferably carbamoyl or sulfomethyl, more preferably carbamoyl,and R₃ is C₁-C₄alkyl, more preferably methyl.

The aliphatic linking group B is, for example, straight-chain orbranched C₂-C₁₂alkylene which is unsubstituted or substituted byhydroxy, C₁-C₄alkoxy, sulfato or sulfo and/or interrupted once orseveral times by —O— or —NR₄—, wherein R₄ is hydrogen or C₁-C₄alkyl,preferably hydrogen, methyl or ethyl, particularly preferably hydrogen.B is preferably straight-chain or branched C₂-C₆alkylene which isunsubstituted or substituted by hydroxy, sulfo or sulfato and,particularly preferably, unsubstituted straight-chain or branchedC₂-C6alkylene. Examples of particularly preferred linking groups B are1,2-ethylene, 1,3-propylene, 2-hydroxy-1,3-propylene, 1,4-butylene,2-methyl-1,5-pentylene, 1,6-hexylene, particularly preferably1,2-propylene and 1,2-ethylene and, very particularly preferably,1,2-ethylene.

X₁ defined as halogen is e.g. fluoro, chloro or bromo.

X₁ defined as C₁-C₄alkoxy is suitably, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy or isobutoxy, preferably methoxy orethoxy and, particularly preferably, methoxy.

X₁ defined as C₁-C₄alkylthio is, for example, methylthio, ethylthio,n-propylthio, isopropylthio or n-butylthio, preferably ethylthio orn-propylthio. The cited radicals are unsubstituted or substituted in thealkyl moiety by hydroxy, carboxy or sulfo. The substituted radicals arepreferred.

X₁ defined as unsubstituted or substituted amino is amino which isunsubstituted or substituted at the N-atom, for example the followingradicals:

N-mono- or N,N-di-C₁-C₄alkylamino, which encompasses both theunsubstituted radicals and the radicals which are substituted in thealkyl moiety, for example by C₁-C₄alkoxy, hydroxy, carboxy, sulfo orsulfato; the radicals substituted in the alkyl moiety being preferred;

C₅-C₇cycloalkylamino, which encompasses both the unsubstituted radicalsand the radicals which are substituted in the cycloalkyl ring, forexample by C₁-C₄alkyl, preferably methyl; of such radicals thecorresponding cyclohexyl radicals are preferred;

phenylamino or N—C₁-C₄alkyl-N-phenylamino, which encompasses both theunsubstituted radicals and the radicals which are substituted in thephenyl ring, for example by C₁-C₄alkyl,

C₁-C₄alkoxy, halogen, carboxy or sulfo; these radicals are preferablyunsubstituted or sulfo-substituted in the phenyl ring.

X₁ defined as a N-heterocycle which may contain further heteroatoms issuitably, for example, morpholino or piperidin-1-yl.

X₁ is preferably fluoro or chloro.

The group U which may be removed with alkali is suitably, for example,—Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group offormula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, morepreferably —Cl or —OSO₃H and, particularly preferably —OSO₃H.

Examples of suitable radicals Y are correspondingly vinyl, β-bromo- orβ-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl,β-chloroethyl or β-sulfatoethyl and, more preferably vinyl orβ-sulfatoethyl.

Hal is preferably bromo.

l and m are each independently of the other preferably the number 2 or3.

Particularly preferably, l is the number 3 and m is the number 2.

Substituents which are customary in dyes are suitable for D. Thefollowing examples may be mentioned: C₁-C₄alkyl, meaning methyl, ethyl,n- or isopropyl, n-, iso-, sec- or tert-butyl; C₁-C₄alkoxy, meaningmethoxy, ethoxy, n- or isopropoxy or n-, iso-, sec- or tert-butoxy;hydroxy-C₁-C₄alkoxy; phenoxy; C₂-C₆alkanoylamino which is unsubstitutedor substituted in the alkyl moiety by hydroxy or C₁-C₄alkoxy, forexample acetylamino, hydroxyacetylamino, methoxyacetylamino orpropionylamino; benzoylamino which is unsubstituted or substituted inthe phenyl moiety by hydroxy, sulfo, halogen, C₁-C₄alkyl or C₁-C₄alkoxy;C₁-C₆alkoxycarbonylamino which is unsubstituted or substituted in thealkyl moiety by hydroxy, C₁-C₄alkyl or C₁-C₄alkoxy; phenoxycarbonylaminowhich is unsubstituted or substituted in the phenyl moiety by hydroxy,C₁-C₄alkyl or C₁-C₄alkoxy; amino; N—C₁-C₄alkyl- orN,N-di-C₁-C₄alkylamino which unsubstituted or substituted in the alkylmoiety by hydroxy, C₁-C₄alkoxy, carboxy, cyano, halogen, sulfo, sulfato,phenyl or sulfophenyl, for example methylamino, ethylamino,N,N-dimethylamino, N,N-diethylamino, β-cyanoethylamino,β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino,γ-sulfo-n-propylamino, β-sulfatoethylamino, N-(3-sulfobenzyl)amino,N-ethyl-N-(3-sulfobenzyl)amino, N-(β-sulfoethyl)-N-benzylamino;cyclohexylamino; N-phenylamino or N-C₁-C₄alkyl-N-phenylamino which isunsubstituted or substituted in the phenyl moiety by nitro, C₁-C₄alkyl,C₁-C₄alkoxy, carboxy, halogen or sulfo; C₁-C₄alkoxycarbonyl, e.g.methoxy- or ethoxycarbonyl; trifluoromethyl; nitro; cyano; halogen,generally meaning e.g. fluoro, bromo or, preferably, chloro; ureido;hydroxy; carboxy; sulfo; sulfomethyl; carbamoyl; N—C₁-C₄alkylcarbamoyl,such as N-methylcarbamoyl or N-ethylcarbamoyl; carbamido; sulfamoyl;N—C₁-C₄alkylsulfamoyl, such as N-methylsulfamoyl or N-ethylsulfamoyl;N-phenylsulfamoyl or N—C₁-C₄alkyl-N-phenylsulfamoyl which isunsubstituted or substituted in the phenyl moiety by sulfo or carboxy;C₁-C₄alkylsulfonyl, such as methyl- or ethylsulfonyl.

Suitable substituents for D are also fibre-reactive radicals.

Fibre-reactive radicals for D are, for example, the radicals of formula(2a), (2b), (2c), (2d) or (2e), wherein Y, Hal, l and m have themeanings and preferred meanings cited above, or (2f) or (2g)

wherein

X₂ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T₁ has each independently of one another the meaning of X₂, asubstituent which is not fibre-reactive or a fibre-reactive radical offormula (4a), (4b), (4c), (4d) or (4e)

 —NH—(CH₂)₂₋₃—SO₂Y  (4a),

—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂Y  (4b),

—NH-arylene-SO₂—Y  (4c),

—NH-arylene-CO—NH—(CH₂)₂₋₃—SO₂—Y  (4d)

or

—NH-arylene-NH—CO—Y₁  (4e),

wherein

R₅ is hydrogen or C₁-C₄alkyl,

arylene is a phenylene or naphthylene radical which is unsubstituted orsubstituted by sulfo, carboxy, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,

T₂ is hydrogen, cyano or halogen,

X₃ is halogen or C₁-C₄alkylsulfonyl,

X₄ is halogen or C₁-C₄alkyl,

Y has the meanings and preferred meanings cited above,

Y₁ is a group —CH(Hal)—CH₂Hal or —C(Hal)═CH₂, and Hal has the meaningsand preferred meanings cited above.

R₅ defined as C₁-C₄alkyl is, for example, methyl, ethyl, n- orisopropyl, n-, iso- or tert-butyl.

R₅ is preferably hydrogen, methyl or ethyl and, particularly preferably,hydrogen.

T₁ defined as a non-reactive substituent may be, for example, hydroxy;C₁-C₄alkoxy; C₁-C₄-alkylthio which is unsubstituted or substituted byhydroxy, carboxy or sulfo; amino; amino which is mono- or disubstitutedby C₁-C,alkyl, wherein the alkyl may be further substituted e.g. bysulfo, sulfato, hydroxy, carboxy or phenyl, preferably by sulfo orhydroxy and may be interrupted by an —O— radical; cyclohexylamino;morpholino; N—C₁-C₄alkyl-N-phenylamino or phenylamino or naphthylamino,wherein phenyl or naphthyl is unsubstituted or substituted by e.g.C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, sulfo or halogen.

Examples of suitable non-reactive substituents T₁ are amino,methylamino, ethylamino, β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino,morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino,1- or 2-naphthylamino, 1-sulfo-2-naphthylamino,4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino,N-methyl-N-phenylamino, methoxy, ethoxy, n- or isopropoxy and hydroxy.

As a radical which is not fibre-reactive, T₁ is preferably C₁-C₄alkoxy;C₁-C₄alkylthio which is unsubstituted or substituted by hydroxy, carboxyor sulfo; hydroxy, amino; N-mono- or N,N-di-C₁-C₄alkylamino which isunsubstituted or substituted in the alkyl moiety by hydroxy, sulfato orsulfo; morpholino; phenylamino or N—C₁-C₄alkyl-N-phenylamino which isunsubstituted or substituted in the phenyl ring by sulfo, carboxy,acetylamino, chloro, methyl or methoxy, wherein the alkyl isunsubstituted or substituted by hydroxy, sulfo or sulfato, ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups.

Particularly preferred radicals T₁ which are not fibre-reactive areamino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino,2-, 3- or 4-sulfophenylamino or N—C₁-C₄alkyl-N-phenylamino.

X₂ defined as halogen is, for example, fluoro, chloro or bromo and,preferably, chloro or fluoro.

Arylene is preferably a phenylene radical, particularly preferably a1,3- or 1,4-phenylene radical which is unsubstituted or substituted e.g.by sulfo, methyl or methoxy.

T₂, X₃ and X₄ defined as halogen are, for example, fluoro, chloro orbromo, preferably chloro or fluoro.

X₃ defined as C₁-C₄alkylsulfonyl is, for example, ethylsulfonyl ormethylsulfonyl, preferably methylsulfonyl.

X₄ defined as C₁-C₄alkyl is, for example, methyl , ethyl, n- orisopropyl, n-, iso- or tert-butyl, preferably methyl.

X₃ and X₄ are preferably each independently of the other chloro orfluoro.

T₂ is preferably cyano or chloro.

In the case of the radicals of formulae (4a) and (4b), Y is preferablyβ-chloroethyl. In the case of the radicals of formulae (4c) and (4d), Yis preferably vinyl or β-sulfatoethyl.

Suitable fibre-reactive radicals D are preferably radicals of formula(2a), (2b), (2c), (2d), (2e), (2f) or (2g), wherein Y is vinyl,β-chloroethyl or β-sulfatoethyl, Hal is bromo, l and m are eachindependently of the other the number 2 or 3, R₅ is hydrogen, and X₂, X₃and X₄ are each independently of one another chloro or fluoro, T₁ is afibre-reactive radical of formula (4c′) or (4d′),

preferably (4c′), wherein Y is vinyl or β-sulfatoethyl, and T₂ is cyanoor chloro.

Those novel reactive dyes are preferred, wherein at least one of theradicals A and D contains a fibre-reactive group.

D is preferably a phenyl or naphthyl radical which may be furthersubstituted by substituents customarily used for dyes, preferably byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo, nitro, carboxy or afibre-reactive radical of formula (2a), (2b), (2c), (2d), (2e), (2f) or(2g), the above meanings and preferred meanings applying to the citedfibre-reactive radicals.

If D carries one or more than one non-reactive substituent, then it ispreferably sulfo, C₁-C₄alkyl, C₁-C₄alkoxy or halogen and, particularlypreferably, sulfo, methyl or methoxy.

D defined as a radical of an unsubstituted or substituted diazocomponent of the benzene or naphthalene series also encompasses monoazoradicals, for example those of formula (5) or (6)

—D*—N═N—K*  (5)

or

D*—N═N—K**—  (6),

preferably of formula (6), wherein D* is the radical of a diazocomponent of the benzene or naphthalene series, K* is the radical of acoupling component of the benzene, naphthalene, pyrazolone,6-hydroxypyridone-(2) or acetoacetic acid arylamide series, and K** isthe radical of a coupling component of the benzene or naphthaleneseries, it being possible for D*, K* and K** to carry substituentscustomarily used in dyes.

Suitable substituents for D*, K* and K** which are not fibre-reactiveare preferably C₁-C₄alkyl or C₁-C₄alkoxy which may be furthersubstituted by hydroxy, C₁-C₄alkoxy, sulfo or sulfato; halogen, carboxy,sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino,ureido, hydroxy, sulfomethyl, C₂-C₄alkanoylamino,C₁-C₄alkylsulfonylamino; benzoylamino which is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen orsulfo, or phenyl which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or sulfo.

Suitable fibre-reactive substituents for D*, K* and K** are preferablythe radicals of formula (2a), (2c), (2d), (2e) or (2f), preferably (2a),the above meanings and preferred meanings applying to the citedradicals.

The monoazo radicals of formula (5) or (6) preferably contain at leastone sulfo group.

Preferred monoazo radicals D of formula (6) correspond to the radicalsof formula (6a), (6b), (6c), (6d), (6e), (6f), (6g), (6h), (6i) or (6j)

wherein (R₆)₀₋₃ is 0 to 3 identical or different substituents from theC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo group, and Z₁ is afibre-reactive radical of formula (2a), (2c), (2d), (2e) or (2f),preferably (2a), (2c), (2d) or (2e), particularly preferably (2a), theabove meanings and preferred meanings applying to the citedfibre-reactive radicals,

wherein (R₆)₀₋₃ has the above meaning, (R₇)₀₋₃ is 0 to 3 identical ordifferent substituents selected from the group consisting of halogen,nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄alkyl,C₁-C₄alkoxy which is unsubstituted or substituted by hydroxy, sulfato orC₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido, hydroxy, carboxy,sulfomethyl, C₁-C₄alkylsulfonylamino and sulfo, and Z₁ has the meaningsand preferred meanings given above.

The numbers at the naphthyl rings of the radicals of formulae (6a),(6b), (6e) and (6f) characterise the possible bonding positions.

Particularly preferred monoazo radicals D of formula (6) correspond tothe radicals of formula (6a), (6b), (6c), (6d) or (6j), in particular(6j), the above meanings applying to (R₆)₀₋₃, (R₇)₀₋₃ and Z₁.

Very particularly preferred monoazo radicals D of formula (6) correspondto the radical of formula (6j′)

wherein

Z₁ may be a radical of formula (2a), wherein Y is vinyl orβ-sulfatoethyl,

(R₆)₀₋₂ is 0 to 2 identical or different substituents from theC₁-C₄alkyl, C_(1-C) ₄alkoxy, halogen, carboxy and sulfo group,preferably methyl, methoxy or sulfo, R₇ is hydrogen, sulfo, orC₁-C₄alkoxy which is unsubstituted or substituted in the alkyl moiety byhydroxy or sulfato, and

R₇′ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino or ureido.

D preferably corresponds to a radical of formula (7)

 wherein

(R₈)₀₋₃ is 0 to 3 identical or different substituents selected from thegroup consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy and sulfo,

Z₂ may be a radical of formula (2a), (2b), (2c), (2d), (2e), (2f) or(2g), wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromo,l and m are each independently of the other the number 2 or 3, R₅ ishydrogen, and X₂, X₃ and X₄ are each independently of one another chloroor fluoro, T₁ is a fibre-reactive radical of formula (4c′) or (4d′),

 preferably (4c′), wherein Y is vinyl or β-sulfatoethyl, and T₂ is cyanoor chloro; or a monoazo radical of formula (6j′), wherein (R₆)₀₋₂, R₇,R₇′ and Z₁ have the meanings and preferred meanings cited for formula(6j′).

D is particularly preferably a radical of formula (7a), (7b), (7c), (7d)or (7e)

wherein

(R₈)₀₋₂ is 0 to 2 identical or different substituents selected from thehalogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo group, preferably methyl,methoxy and sulfo,

Y₁ is a radical —CH(Br)—CH₂—Br or —C(Br)═CH₂,

Y is vinyl, β-chloroethyl or β-sulfatoethyl, preferably vinyl orβ-sulfatoethyl, and

m is the number 2 or 3, preferably 2.

The numbers in the radicals of formulae (7a), (7c), (7d) and (7e)characterise the possible bonding positions of the fibre-reactiveradical.

D is preferably a radical of formula (7a), (7b) or (7e).

Suitable radicals A correspond, for example, to a radical of formula(7), wherein (R₈)₀₋₃ has the above meanings, and Z₂ is a radical offormula (2a), (2b), (2c), (2d) or (2e), the above meanings and preferredmeanings applying to Y, Hal, l and m; preferably a radical of formula(7a), (7b), (7c) or (7d), in particular (7a) or (7b), wherein (R₈)₀₋₂,Y, Y₁ and m have the meanings and preferred meanings given for formulae(7a), (7b), (7c) and (7d).

Suitable radicals A containing no fibre-reactive group are, for example,the following radicals: 2-,3- or 4-sulfophenyl, 2,4-di-sulfophenyl,2,5-di-sulfophenyl, 1,5-di-sulfonaphth-2-yl or 1,6-di-sulfonaphth-2-yland, preferably, 2,5-di-sulfophenyl.

A is preferably phenyl which is substituted by 1 to 2 identical ordifferent substituents selected from the methyl, methoxy, sulfo andfibre-reactive group of formula (2a), wherein Y is vinyl orβ-sulfatoethyl.

A is particularly preferably 2,5-di-sulfophenyl or4-(β-sulfatoethylsulfonyl)phenyl.

In a preferred embodiment of this invention, the novel reactive dyescorrespond to formula (1a)

wherein

A is phenyl which is substituted by 1 to 2 identical or differentsubstituents selected from the group consisting of methyl, methoxy,sulfo and fibre-reactive group of formula —SO₂—Y (2a), wherein Y isvinyl or β-sulfatoethyl,

B is straight-chain or branched C₂-C₆alkylene, preferably ethylene,

D corresponds to a radical of formula (7a), (7b), (7c), (7d) or (7e),preferably to (7a), (7b) or (7e), wherein (R₈)₀₋₂, Y, Y₁ and m have theabove meanings and preferred meanings,

R₂ is carbamoyl or sulfomethyl, preferably carbamoyl,

R is hydrogen or corresponds to a radical of formula (3a)

 wherein B, D and R₂ have the meanings and preferred meanings citedabove, and X₁ is chloro or fluoro.

This invention also relates to a process for the preparation of thenovel reactive dyes, which comprises reacting about 1 molar equivalenteach of an amine of formula (8)

of a compound of formula (9)

of a compound of formula (10)

in any sequence with each other, wherein A, B, D, R₁, R₂, R₃ and R havethe above meanings and X is halogen, preferably fluoro or chloro.

The individual process steps described above can be carried out indifferent order, some of them, where appropriate, also simultaneously,so that different process variants are possible. The reaction is usuallycarried out in stepwise succession, the sequence of the single reactionsbetween the individual reaction components advantageously beingdependent on the particular conditions.

One process variant is that, wherein a compound of formula (8) iscondensed with cyanuric chloride or cyanuric fluoride and the productobtained is reacted with a compound of formula (10).

The condensation reactions between the compounds of formulae (8), (9)and (10) are usually carried out in analogy to known processes, normallyin aqueous solution at temperatures in the range from e.g. 0 to 35° C.and at a pH from e.g. 3 to 8.5. In the process in it also possible toreplace the compound of formula (10) with the corresponding precursor offormula (11)

and to complete the azo chromophore only in the further course of theprocess by diazotisation of an amine of formula (12)

D—NH₂  (12)

and subsequent coupling reaction. B, D, R₂, R₃ and R have the meaningsgiven above.

The compound of formula (10) is obtained by diazotising an amine offormula (12) and coupling the diazonium compound so obtained to acompound of formula (11).

The diazotisation of the compound of formula (12) and its coupling tothe compound of formula (11), or to the condensate obtained according tothe above procedure from the compound of formula (11), is carried out incustomary manner, for example by diazotising the compound of formula(12) in mineral acidic solution, e.g. in hydrochloric solution, with anitrite, e.g. sodium nitrite, at a low temperature, e.g. from 0 to 5°C., and then coupling the compound so obtained at a neutral to slightlyacid pH, e.g. at a pH from 3 to 8.5, and at low temperatures, e.g. from0 to 30° C., with the corresponding coupling component.

The compounds of formulae (8), (11) and (12) are known or can beprepared in analogy to known compounds.

The triazinyl compounds obtainable according to the process describedabove contain a halogen atom which, by reaction with a compound offormula X₁—H and at an elevated temperature, preferably from 20 to 70°C., and at a neutral to slightly alkaline pH which, depending on thecompound of formula X₁—H used, may be e.g. from 7 to 9, can be convertedinto a X₁ group, wherein X₁ has the meanings given above except halogen.It is advantageous to use an excess of the compound of formula X₁—H.

The end product may also be subjected to a conversion reaction. Such aconversion reaction is, for example, the conversion of a vinylatablereactive group present in A and/or D into its vinyl form by treatmentwith dilute sodium hydroxide solution, for example the conversion of theβ-sulfatoethylsulfonyl or β-chloroethylsulfonyl group into the vinylsulfonyl radical. Such reactions are known per se.

The novel compounds of formula (1) are suitable as dyes for dyeing orprinting a very wide range of materials, such as hydroxylgroup-containing or nitrogen-containing fibre materials. Typicalexamples of such materials are silk, leather, wool, polyamide fibres andpolyurethanes. The novel reactive dyes are particularly suitable fordyeing and printing cellulosic fibre materials of all kinds. Suchcellulosic fibre materials are, for example, natural cellulose fibres,such as cotton, linen and hemp, as well as cellulose and regeneratedcellulose, preferably cotton. The novel reactive dyes are also suitablefor dyeing or printing cellulose-containing blended fabrics, e.g. blendsof cotton and polyamide fibres or, in particular, cotton/polyester fibreblends.

The novel reactive dyes may applied and fixed to the fibre material indifferent manners, preferably in the form of aqueous dye solutions andprinting pastes. They are suitable both for the exhaust process and fordyeing by the pad-dyeing process, in which the goods are impregnatedwith aqueous dye solutions which may contain salts, and the dyes arefixed after treatment with alkali, or in the presence of alkali, with orwithout the application of heat or by being stored for several hours atroom temperature. After fixation, the dyeings or prints are thoroughlyrinsed with cold and hot water, where appropriate with addition of adispersant promoting the diffusion of the unfixed dye.

The novel reactive dyes are distinguished by high reactivity, goodfixation and excellent build-up. They can therefore be used by theexhaust dyeing process at low dyeing temperatures and require only shortsteaming times in the pad-steam process. The degrees of fixation arehigh, and unfixed dye can be readily washed off. The differences betweendegree of exhaustion and degree of fixation is remarkably small, i.e.the soap loss is very small. The dyes of this invention are alsoparticularly suitable for printing, especially on cotton, and forprinting nitrogen-containing fibres, e.g. wool or silk, or blendscontaining wool or silk.

The dyeings and prints obtained with the dyes of this invention haveexcellent tinctorial strength and excellent fibre-dye bond stabilityboth in the acid and in the alkaline range, and they also have goodlightfastness and excellent wetfastness properties such as fastness towashing, water, sea-water, cross-dyeing and perspiration, as well asgood fastness to pleating, ironing and rubbing.

The following Examples illustrate the invention in more detail.Temperatures are given in degrees Celsius, and parts and percentages areby weight, unless otherwise stated. The ratio of parts by weight toparts by volume is the same as that of the kilogram to the liter.

EXAMPLE 1

373 Parts of ethyl cyanoacetate are slowly added to 152 parts ofdiethylene triamine at 80 to 85° C. After the addition is complete, theresulting ethanol is distilled off under a weak vacuum. Subsequently,750 parts of water are added to the reaction mixture and this mixture isdistilled again under a weak vacuum. After charging the residue with 429parts of ethyl acetate and 255 parts of a 30% aqueous ammonia solution,the temperature is raised to 90 to 95° C. and the resulting water isdistilled off under a weak vacuum. Subsequently, the reaction mixture isadded to 1000 parts of an aqueous potassium chloride solution and theprecipitated product is subjected to filtration and then dried. Thisyields 771 parts of a compound of formula

from which the compound of formula

is obtained via saponification with sulfuric acid.

EXAMPLE 2

204 parts of ethyl cyanoacetate are added slowly to 322 parts ofethylenediamine at 80° C. After the addition is complete, the resultingethanol is distilled off under a weak vacuum. Subsequently, 720 parts ofwater, 234 parts of ethyl acetate and 162 parts of a 30% aqueous ammoniasolution are added to the reaction mixture. The temperature is raised to90 to 100° C. and the batch is refluxed for 2 hours. Subsequently, thehot reaction mixture is added to 1800 parts of an ice/water mixture. ThepH is adjusted to 7 with hydrochloric acid and the product whichprecipitates at room temperature is subjected to filtration and thendried. This yields 312 parts of a compound of formula

from which the compound of formula

EXAMPLE 3

42.2 Parts of an amine of formula A₁₀—NH₂, wherein A₁₀ is a radical offormula

are dissolved in 200 parts of water with addition of a 20% sodiumcarbonate solution at room temperature and at pH 3.2, and a solution of1.5 g of disodium hydrogenphosphate in 20 parts of water is then added.21.3 Parts of cyanuric fluoride are added dropwise to this solution at atemperature below 2° C. and at pH 6.2, which pH is kept constant byaddition of a 2 N sodium hydroxide solution. A solution of 48.6 parts ofthe compound obtained according to Example 1 in 200 parts of water isadded to the suspension so obtained, the pH being kept at 6.8 to 7.5through addition of a 20% sodium carbonate solution and the temperaturebeing kept at 10 to 20° C. To complete the reaction, the mixture isstirred for one hour at room temperature and the pH is then adjusted to6.2 with 2 N of hydrochloric acid. This yields 700 parts of a solutioncontaining a compound of formula

EXAMPLE 4

A neutral solution of 18.2 parts of an amine of formula D₁₀—NH₂ in 150parts of water, wherein D₁₀ is a radical of formula

is charged with 15 parts of a 4 N sodium nitrite solution. A mixtureconsisting of 30 parts of ice/water and 15 parts of conc. hydrochloricacid is added to this solution at 0° C. The reaction mixture is stirredfor one hour at 0° C. This mixture is then charged with 175 parts of thesolution obtained according to Example 3 at 2 to 6° C., the pH beingadjusted with sodium hydrogencarbonate first to 6.2 and then with a 20%sodium carbonate solution to 8.5. To complete the reaction, the mixtureis stirred for one hour at 6 to 20° C. and the pH is then adjusted to6.2 with 2 N hydrochloric acid. The solution so obtained is then freedfrom salt by dialysis and is concentrated by evaporation, yielding 30.9parts of a compound which, in the form of the free acid, corresponds toformula (101)

and which dyes cotton in a yellow shade having good allround fastnessproperties.

EXAMPLES 5 TO 40

In analogy to the procedure described in Examples 3 and 4, dyes of thefollowing general formula (102) are obtained

if the amine of formula A₁₀—NH₂ is replaced with the equimolar amount ofan amine of formula A_(xy)—NH₂ and/or if the amine of formula D₁₀—NH₂ isreplaced with the equimolar amount of an amine of formula D_(xy)—NH₂,wherein A_(xy) and D_(xy) each correspond to the radicals listed inTable 2, these radicals each having the meanings cited in Examples 3, 4and in Table 1. The dyes dye cotton and wool in a yellowish orange shadehaving good allround fastness properties.

TABLE 1 Amine Amine A_(xy)—NH₂ A_(xy) D_(xy)—NH₂ D_(xy) A₁₁—NH₂

D₁₁—NH₂

A₁₂—NH₂

D₁₂—NH₂

A₁₃—NH₂

D₁₃—NH₂

A₁₄—NH₂

D₁₄—NH₂

A₁₅—NH₂

D₁₅—NH₂

A₁₆—NH₂

D₁₆—NH₂

A₁₇—NH₂

D₁₇—NH₂

A₁₈—NH₂

D₁₈—NH₂

A₁₉—NH₂

D₁₉—NH₂

A₂₀—NH₂

D₂₀—NH₂

A₂₁—NH₂

D₂₁—NH₂

A₂₂—NH₂

D₂₂—NH₂

A₂₃—NH₂

D₂₃—NH₂

A₂₄—NH₂

D₂₄—NH₂

A₂₅—NH₂

D₂₅—NH₂

A₂₆—NH₂

D₂₆—NH₂

A₂₇—NH₂

D₂₇—NH₂

A₂₈—NH₂

D₂₈—NH₂

A₂₉—NH₂

D₂₉—NH₂

A₃₀—NH₂

D₃₀—NH₂

A₃₁—NH₂

D₃₁—NH₂

A₃₂—NH₂

D₃₂—NH₂

A₃₃—NH₂

D₃₃—NH₂

D₃₄—NH₂

D_(35a)—NH₂- D_(35c)—NH₂ =

D_(36a)—NH₂- D_(36c)—NH₂ =

T₁: D_(35a)/D_(36a)

D_(35b)/D_(36b)

D_(35c)/D_(36c)

TABLE 2 Example A_(xy) D_(xy) 5 A₁₀ D₁₁ 6 A₁₀ D₁₂ 7 A₁₀ D₁₃ 8 A₁₇ D₁₁ 9A₁₇ D₁₂ 10 A₁₇ D₁₃ 11 A₁₈ D₁₁ 12 A₁₈ D₁₂ 13 A₁₈ D₁₃ 14 A₁₉ D₁₁ 15 A₁₉D₁₂ 16 A₁₉ D₁₃ 17 A₂₀ D₁₁ 18 A₂₀ D₁₃ 19 A₂₁ D₁₁ 20 A₂₁ D₁₃ 21 A₂₂ D₁₁ 22A₂₂ D₁₃ 23 A₂₃ D₁₁ 24 A₂₃ D₁₃ 25 A₂₄ D₁₁ 26 A₂₄ D₁₃ 27 A₂₅ D₁₁ 28 A₂₅D₁₃ 29 A₂₆ D₁₁ 30 A₂₆ D₁₃ 31 A₂₇ D₁₁ 32 A₂₇ D₁₃ 33 A₂₈ D₁₁ 34 A₂₈ D₁₃ 35A₂₉ D₁₁ 36 A₂₉ D₁₂ 37 A₃₀ D₁₁ 38 A₃₀ D₁₃ 39 A₃₁ D₁₁ 40 A₃₁ D₁₂

EXAMPLE 41

20.3 Parts of cyanuric chloride are thoroughly stirred in 150 parts ofwater with addition of a wetting agent at a temperature from 0° C. 27.8Parts of aniline-2,5-disulfonic acid (A₁₁—NH₂) are added to thismixture. The temperature is kept for 5 hours at 0 to 5 ° C. and the pHis kept at 3 to 4 by addition of 2 N sodium hydroxide solution. The pHis then adjusted to 7 and the mixture is clarified by filtration. Theresulting filtrate is charged over 2.5 hours with 40.5 parts of thecompound obtained according to Example 1, the pH being kept at 7.5 to8.5 by addition of a 2 N sodium hydroxide solution, the temperaturerising to 36° C. To complete the reaction, the mixture is stirred forone hour at room temperature and the pH is then adjusted to 7 with 2 Nhydrochloric acid. This yields 714 parts of a solution containing acompound which, in the form of the free acid, corresponds to formula

EXAMPLE 42

A neutral solution of 14.1 parts of an amine of formula D₁₄—NH₂ in 120parts of water, wherein D₁₄ is a radical of formula

is charged with 12.5 parts of a 4 N sodium nitrite solution. A mixtureconsisting of 30 parts of ice/water and 12.5 parts of conc. hydrochloricacid is added to this solution at 0° C. The reaction mixture is stirredfor one hour at 0 to 5° C. and is then added to 179 parts of thesolution obtained according to Example 41 at 5 to 7° C., the pH beingadjusted over 30 minutes to 6 with sodium hydrogencarbonate. To completethe reaction, the mixture is stirred for another 30 minutes at 7 to 15°C. The resulting solution is freed from salt by dialysis andconcentrated by evaporation. This yields 24.2 parts of a compound which,in the form of the free acid, corresponds to formula (103)

and which dyes cotton in a yellow shade having good allround fastnessproperties.

EXAMPLES 43 TO 75

In analogy to the procedure described in Examples 41 and 42, the dyes ofthe following general formula (104) are obtained

if aniline-2,5-disulfonic acid (A₁₁—NH₂) is replaced with the equimolaramount of an amine of formula A_(xy)—NH₂ and/or if an amine of formulaD₁₄—NH₂ is replaced with the equimolar amount of an amine of formulaD_(xy)—NH₂, wherein A_(xy) and D_(xy) each correspond to the radicalslisted in Table 3, each of these radicals having the meanings cited inTable 1. The dyes dye cotton and wool in a yellowish orange shade havinggood allround fastness properties.

TABLE 3 Example A_(xy) D_(xy) 43 A₁₁ D₂₀ 44 A₁₁ D₂₁ 45 A₁₁ D₂₂ 46 A₁₁D₁₇ 47 A₁₁ D₁₈ 48 A₁₁ D₂₅ 49 A₁₁ D₂₇ 50 A₁₁ D₂₉ 51 A₁₁ D₁₉ 52 A₁₂ D₂₀ 53A₁₅ D₁₅ 54 A₁₅ D₁₆ 55 A₁₅ D₂₃ 56 A₁₅ D₂₄ 57 A₁₅ D₂₆ 58 A₁₆ D₂₈ 59 A₁₆D₁₆ 60 A₁₃ D₁₅ 61 A₁₃ D₁₆ 62 A₁₃ D₂₃ 63 A₁₃ D₂₄ 64 A₁₃ D₂₆ 65 A₁₃ D₂₈ 66A₁₃ D₃₀ 67 A₁₃ D₃₁ 68 A₁₄ D₁₅ 69 A₁₄ D₁₆ 70 A₁₁ D_(35a) 71 A₁₁ D_(35b)72 A₁₁ D_(36a) 73 A₁₂ D_(36c) 74 A₁₂ D₃₃ 75 A₁₁ D₃₄

EXAMPLE 76

30.4 Parts of aniline-2,5-disulfonic acid (A₁₁—NH₂) are dissolved in 300parts of water until neutral and a solution of 1.5 g of disodiumhydrogenphosphate in 20 parts of water is added. This solution ischarged at a temperature below 2° C. and at pH 6.8 with 17 parts ofcyanuric fluoride, the pH being kept constant by addition of 2 N sodiumhydroxide solution. The solution so obtained is charged with 21.1 partsof the compound obtained according to Example 2 over 2 hours, the pHbeing kept at 7.5 to 8.5 with a 2 N sodium hydroxide solution and thetemperature rising to 22° C. This yields 648 parts of a solution whichcontains a compound of formula

EXAMPLE 77

A neutral solution of 25.2 parts of an amine of formula D_(35a)—NH₂ in300 parts of water, wherein D_(35a) is a radical of formula

is charged with 44 parts of a 1 N sodium nitrite solute. The pH of thissolution is adjusted to 1.6 at 0° C. with 2 N hydrochloric acid and thesolution is stirred for one hour at 0 to 5° C. This mixture is chargedat 2° C. with 285 parts of the solution obtained according to Example76. The pH is adjusted over 30 minutes with a 20% sodium carbonatesolution to 8.5 and, after the reaction is complete, with 2 Nhydrochloric acid to 6.4. The resulting solution is charged with 280parts of acetone and 90 parts of potassium chloride. The precipitate issubjected to filtration and is then washed with acetone and dried. Thisyields 41.3 parts of a compound which, in the form of the free acid,corresponds to formula (105)

and which dyes cotton in a yellow shade having good allround fastnessproperties.

EXAMPLES 78 TO 102

In analogy to the procedure described in Examples 76 and 77, the dyesfollowing general formula are obtained (106)

if aniline-2,5-disulfonic acid (A₁₁—NH₂) is replaced with the equimolaramount of an amine of formula A_(xy)—NH₂ and/or if an amine of formulaD_(35a)—NH₂ is replaced with the equimolar amount of an amine of formulaD_(xy)—NH₂, wherein A_(xy) and D_(xy) each correspond to the radicalslisted in Table 4, which radicals have the meanings cited in theExamples 3 and 4 and in Table 1. The dyes dye cotton and wool in ayellowish orange shade having good allround fastness properties.

TABLE 4 Example A_(xy) D_(xy) 78 A₁₁ D_(36a) 79 A₁₁ D_(35b) 80 A₁₁D_(35c) 81 A₁₂ D_(36a) 82 A₁₁ D₂₃ 83 A₁₁ D₂₄ 84 A₁₁ D₁₄ 85 A₁₅ D₁₅ 86A₁₁ D₁₇ 87 A₁₀ D₁₀ 88 A₁₀ D₁₂ 89 A₂₉ D₁₀ 90 A₃₂ D₁₁ 91 A₁₃ D₁₅ 92 A₁₃D₁₆ 93 A₁₄ D₂₃ 94 A₁₃ D₂₆ 95 A₁₃ D₂₈ 96 A₁₃ D₃₂ 97 A₁₃ D₃₄ 98 A₁₁ D₁₈ 99A₁₇ D₁₃ 100 A₁₇ D₁₁ 101 A₁₈ D₁₀ 102 A₃₃ D₁₀

Dyeing Instruction I

100 Parts of cotton fabric are placed at 60° C. in 1500 parts of a dyeliquor containing 45 g/l of sodium chloride and 2 parts of the reactivedye obtained according to Example 4. After 45 minutes at 60° C., 20 g/lof calcined sodium carbonate are added. Dyeing is continued for another45 minutes at this temperature. The dyed goods are then rinsed, soapedat the boil for a quarter of an hour with a non-ionic detergent, rinsedagain and dried.

Alternatively to the above instruction, it is also possible to dye at80° C. instead of at 60° C.

Dyeing Instruction II

0.1 Part of the dye of Example 4 is dissolved in 200 parts of water andthen 0.5 part of sodium sulfate, 0.1 part of a levelling agent (based onthe condensate from a higher aliphatic amine and ethylene oxide) and 0.5part of sodium acetate are added. The pH is then adjusted to 5.5 withacetic acid (80%). The dye bath is heated for 10 minutes to 50° C. and10 parts of a wool fabric are then added. The dye bath is then heatedover about 50 minutes to 100° C. and dyeing is carried out at thistemperature for 60 minutes. The dye bath is then allowed to cool to 90°C. and the dyed goods are taken out. The wool fabric is washed with warmand cold water and is then spun and dried.

Printing Instruction

3 Parts of the dye obtained in Example 4 are sprinkled, with rapidstirring, into 100 parts of a stock thickening which contains 50 partsof 5 % sodium alginate thickening, 27.8 parts of water, 20 parts ofurea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumhydrogen carbonate. A cotton fabric is printed with the printing pasteso obtained and dried. The printed fabric is steamed for 2 minutes at102° C. in saturated steam, then rinsed, if necessary soaped at theboil, then rinsed once more and subsequently dried.

What is claimed is:
 1. A reactive dye of formula (1)

wherein A is phenyl or naphthyl, each of which is unsubstituted orsubstituted by halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, sulfo or afibre-reactive group of formula (2a), (2b), (2c), (2d) or (2e)—SO₂—Y  (2a), —NH—CO—(CH₂)_(l)—SO₂—Y  (2b), —CONH—(CH₂)_(m)—SO₂—Y  (2c),—NH—CO—CH(Hal)—CH₂Hal  (2d) or —NH—CO—C(Hal)═CH₂  (2e), B is analiphatic linking group, D is the radical of a diazo component of thebenzene or naphthalene series, R₁ is hydrogen or unsubstituted orsubstituted C₁-C₄alkyl, R₂ is hydrogen, cyano, carbamoyl or sulfomethyl,R₃ is hydrogen or C₁-C₄alkyl, R corresponds to a radical of formula (3)

 wherein B, D, R₂ and R₃ have the meanings cited above, X₁ is halogen,hydroxy, C₁-C₄alkoxy, unsubstituted or substituted C₁-C₄alkylthio orunsubstituted or substituted amino, or a N-heterocycle which may containadditional heteroatoms, Hal is chloro or bromo, Y is vinyl or a—CH₂—CH₂—U radical, U is a group which is removable with alkali, and land m are each independently of the other the number 2, 3 or
 4. 2. Areactive dye according to claim 1, wherein A is phenyl which issubstituted by 1 to 2 identical or different substituents selected fromthe group consisting of methyl, methoxy, sulfo and a fibre-reactivegroup of formula (2a), wherein Y is vinyl or β-sulfatoethyl.
 3. Areactive dye according to claim 1, wherein B is straight-chain orbranched C₂-C₆alkylene.
 4. A reactive dye according to claim 1, whereinR₁ is hydrogen or C₁-C₄alkyl.
 5. A reactive dye according to claim 1,wherein R₁ is hydrogen.
 6. A reactive dye according to claim 1, whereinR₂ is carbamoyl or sulfomethyl, and R₃ is C₁-C₄alkyl.
 7. A process forthe preparation of a reactive dye according to claim 1, which comprisesreacting about 1 molar equivalent each of an amine of formula (8)

of a compound of formula (9)

of a compound of formula (10)

in any sequence with each other, wherein A, B, D, R₁, R₂, R₃ and R havethe meanings given in claim 1 and X is halogen.
 8. A reactive dyeaccording to claim 1, wherein X₁ is chloro or fluoro.
 9. A reactive dyeaccording to claim 1, wherein at least one of A and D contains afibre-reactive group.
 10. A reactive dye according to claim 1, wherein Dis a radical of formula (7) or (6j′)

 wherein (R₈)₀₋₃ is 0 to 3 identical or different substituents selectedfrom the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxyand sulfo, Z₂ may be a radical of formula (2a), (2b), (2c), (2d), (2e),(2f) or (2g) —SO₂—Y  (2a), —NH—CO—(CH₂)_(l)—SO₂—Y  (2b),—CONH—(CH₂)_(m)—SO₂—Y  (2c), —NH—CO—CH(Hal)—CH₂Hal  (2d),—NH—CO—C(Hal)═CH₂  (2e),

 wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromo, land m are each independently of the other the number 2 or 3, R₅ ishydrogen and X₂, X₃ and X₄ are each independently of one another chloroor fluoro, T₁ is a fibre-reactive radical of formula (4c′) or (4d′),

wherein Y is vinyl or β-sulfatoethyl, and T₂ is cyano or chloro; or

 wherein Z₁ may be a radical of formula (2a), wherein Y is vinyl orβ-sulfatoethyl, (R₆)₀₋₂ is 0 to 2 identical or different substituentsfrom the C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo group, R₇is hydrogen, sulfo, or C₁-C₄alkoxy which is unsubstituted or substitutedin the alkyl moiety by hydroxy or sulfato, and R₇′ is hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino or ureido.
 11. A reactivedye according to claim 1, wherein D corresponds to a radical of formula(7a), (7b), (7c), (7d) or (7e)

wherein (R₈)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo,Y₁ is a —CH(Br)—CH₂—Br or —C(Br)═CH₂ radical, Y is vinyl, β-chloroethylor β-sulfatoethyl, and m is the number 2 or
 3. 12. A reactive dyeaccording to claim 11, which corresponds to formula (1a)

wherein A is phenyl which is substituted by 1 to 2 identical ordifferent substituents selected from the group consisting of methyl,methoxy, sulfo and the fibre-reactive group of formula —SO₂—Y (2a),wherein Y is vinyl or β-sulfatoethyl, B is straight-chain or branchedC₂-C₆alkylene, D corresponds to a radical of formula (7a), (7b), (7c),(7d) or (7e), wherein (R₈)₀₋₂, Y, Y₁ and m have the meanings given inclaim 11, R₂ is carbamoyl or sulfomethyl, R corresponds to a radical offormula (3a)

 wherein B, D and R₂ have the meanings cited above, and X₁ is chloro orfluoro.
 13. A process for dyeing or printing a fibre material containinghydroxyl groups or nitrogen, which comprises applying to said fibrematerial a reactive dye of formula (1) according to claim
 1. 14. Aprocess according to claim 13, wherein said fibre material is cellulosicfibre material.
 15. A process according to claim 13, wherein said fibrematerial is cotton.